Condensation products of the naphthostyril series and process of preparing the same



, stltution product I: @Patented June 3, 1930 I.

enon'e KRKNZLEIN, max' GERMANY, assrenoas 'ro, coaroiwrrorrornnmwazaooma'nnsarron rnonucrs NoDrawin'g'. Applicationflled November 21, 1 927,SeriaI'No. 234,908,

.A The. present invention, relates to condensationproducts of thenaphthostyril series and i which in the compound :when complete isprocess ofv preparing the same.

' We have found that products are obtained which are useful asdyestufl's, or as intermediate products for the manufacture ofdyestuffs, by condensing-naphthostyril,or a subthereof, with an aromaticcompound containing at least-one reactive nuclear hydrogen atom,particularly with a 'monovalent or polyvalent phenol or with a tertiaryamine containing the group wherein at least one of the three C atomsbelongs to an aromatic nucleus. Suitablecon-- for example, phosphorusdensing agents are,

chloride or the like. The

halides and thionyl condensation products produced from the saidaminesare basic dyestufl's and have an enhanced fastness to light ascompared with dyestuffs. The products ,producedby means of thepolyhydricphenols, such as pyrogallol, oxyhydroquinone,

gallic acid and resorcinol or the like, are

of being chromed, Both dyestuffs capable products obtained the basiccondensation from the amines and the acid condensation henols, can

wool dyeproducts obtained from the p easily be sulfonated to yield acidstugs of valuable properties.-

.our new process'may following formula:

wherein 3 stands for the residue of an acid or a sulfo group substitutedfor a nuclear 'methylbenzylaniline,

TENT. orlca or run nsrnraosrymr. seams AND frnocnss or rmsnmernn SAME Iand; in Germany November 80, 1928.

hydrogen atom, R for an aromatic compound deprived of that nuclearhydrogen atom color base is dissolved in hot water which is acid, and

slightly acid with hydrochlorid dyestufl' is after the solution hascooled the with exclusion of precipitated in crystalline condition byad-- dition of sodium acetate. It is obtained in a pure state byreciystallizatiolifrom dilute hydrochloric acid. It dyes cottonmordan'ted with tannin, or wool, blue violet.

The dyestuif has probably the following' formula e. condensationproducts obtainable by be represented by the r I analogous manner whendiethylaniline, methylcyclohexylani-- ethylbenz laniline,dibenzylaniline,

line,

-methyld1phenylamine or ethylcarbazole,

' the like is substituted for the dimethylaniline Dialkyla-naphthylamine and dialkyl-flmaph'thylamine yield.

used in the example.

pure blue dyestufis...

so. Dyestufls of similar tints are obtained in By substituting for thediethylaminophe-- netol meta-ehlorodimethylaniline ormetachlorodiethylaniline dyestuffs of more bluish tints are obtained.

3. 17 parts of naphthostyril, 15 parts of pyrogallol and 12 parts ofphosphorus oxychloride are mixed with 100 parts of chlorobenzene and themixture is heated for some solves easily in water to a dark dry it isbronze and dissolving. easily in water to a blue solution; it dyescotton mordanted with tannin, silkfpa'per and the like dark bluegrey. 5.By substituting tetra-methyl-meta-phepaper and the like reddish blue.

a dark powder having the lustre of 6. 15 parts of naphthostyril, 50parts of toluene, 20 parts of N.N-dimethyl -L2.3'.4=-"

tetrahydroquinoxaline (German patent application J. 30698) and 10 partsof phos stirred together first.

phorus oxychloride are at the temperature of the room and the mixture inthen heated for about-6 hours at 100 C. The mass is introduced intowater, made alkaline with sodium carbonate and treated with steam. Theresidue is dried, dissolved in 10 times its weight of toluene andprecipitated from this solution in the form'of its salt by means ofgaseous hydrochloric acid. When dry it forms a black powder whichdisblue solution. Cotton mordanted with tannin, paper and the like aredyed by it blue-black tints.

The following constitutional formulas may be attributed to the dyestuii:

or 0 H01 Cl more simply v C I- PCB! CHa-N N-CH; CHr-N N-CH3 hours at 110C. The solvent is expelled by steam and the dyestufl dissolved in hotwater containing some hydrochloric acid. On standing in the cold thedyestufi separates from the solution in the form of red-yellow needles;it has the character of a mordant dyestufi. 4

4. 20 parts of tetra-methyl-ortho-phenylenediamine, 10 parts ofphosphorus oxychloride and 15 parts of naphthostyril are stirred in 50parts of toluene for 5 hours at ordinary temperature and the mixture isthen heated for 8 hours to 100 C. The mass is introduced 1nto water,rendered alkaline with sodium carbonate and treated with steam. Theresidue is extracted with dilute hydrochloric acid and the colour baseprecipitated by addition of sodium acetate, filtered, washed and dried;it is dissolved in toluene and precipitated from the solution in theform of a salt by means of gaseous hydrochloric acid. When 7. Thedyestufi Example 6 by the condensation of naphthostyril andN.N-din'iethyltetraliydroquinoxaline is stirred in 10 times its weightof sulfuric acid containing anhydride, at 30 C. until a test-sampleshows that the mixture dissolves in sodium carbonate. The mass is thenpoured on ice, filtered and salted out. The resulting dyestufi'dissolves in water to a reddish-blue solution and dyes wool blue tints.

8. 10 parts of the condensation product from naphthostyril. anddimethylaniline are sulfonated by gently warming with 100 parts of oleumcontaining 20 per cent. of anhydride, the solution is poured on ice andthe sulfonic acid of the dyestufi' is separated by addition of commonsalt. The product dyes wool violet.

9. The condensation product from naphthostyril and pyragallol issulfonated even at obtained according to ordinary temperature by meansof oleum of IQ per cent. strength. The sulfonic acid of the dyestufi',separated in the from the mixture, dyes wool changes towards brown onwashing and when after-chromed becomes a brilliantred-orange.

'We claim: i

1. Theprocess of preparing condensation products of the naphthostyrllseries, which lowing formula:

consists in condensing a compound of the following formula:

wherein :2: stands for anysubstituent'with an aromatic. compound,containing at least one reactive nuclear hydrogen atom, by means of aphosphorus halide. 2. e process of consists in condensing a compound ofthe folwherein a stands for any 'substituent with an aromatic compound,containing at least one solvent.

. a phosphorus halide.

reactive nuclear hydrogen atom, by means of a phosphorus I reparingcondensation 3. The process of thostyril series, which products of thenap consists in condensing naphthostyril with an aromatic compound,containing at least one reactlve nuclear hydrogen atom, by means of 4.The process of preparing-condensation products of aromatic compoundcontaining at least one reactive nuclear hydrogen atom, by means ofphosphorus oxychloride.

he process of perparing condensation products of the naphthostyrilseries, which consists in 'COIldeIlSlIl naphthostyril with a tertiaryamine which contains the group wherein at least one of the 3 C atomsbelongs to an aromatic nucleus containing at least one reactive nuclearhydrogen atom, of a phosphorus halide.

Theprocess of reparing condensation products of the nap by .means usualmanner yellow, which preparing condensation products of thenaphthostyril series, which halide in the presence of a.

c the naphthostyril series, which consists in condensingnaphthostyrilwith an thostyrilseries, which.

consists in condensing naphthostyril with a tertiary amine whichcontains the group of the following formula:

. ,RCH; (IQ/ I by means of a phosphorus halide.

The process of preparing condensation products of the naphthostyrilseries, which consists in condensing naphthostyril with of thefollowin'gformula 'N.N 7 dimethyl 1.2.3.4-tetrahydroquinoxaline by means ofphosphorus oxychloride.

9. The process. of products of the naphthostyril series, wh ch consistsin condensing naphthostyril w th KN-dimethyl 1.2.3.4-tetrahydroquinoxal1ne of the following formula:

by'means ofphosphorus oxyehloride, with the addition of toluene as asolvent.

1 0, As new products, the compounds of'the following formula wherein '2]stands for the residue of an acid or a sul 0 group substituted. for anuclear preparing condensation f hydrogen atom, R for an aromaticcompound deprived of that nuclear hydrogen atom which in the compoundwhen complete is articularly reactive, said products being yestuffswhich are soluble in water.

11. As new products, the compounds of the following formula:

larly reactive, the amine containing the wherein at least one of the 3 Catoms belongs cotton mordanted with tannin, paper or the like,blue-black tints.

In testimony whereof, we aflix our signatures.

to anaromatic nucleus, said products being dyestuffs which are solublein water.

12. As new products, the compounds of the following formula:

CHaN N-CH;

wherein 3 stands for an acid residue or a sulfo group substituted for anuclear hydrogen atom, said products being dyestufis soluble in waterand dyeing. the fiber dark-blue tints.

following formula:

said product'being a dyes'tufi forming in a dry state a black powder,readily dissolving in water to a dark-blue'solution and dyeing 13. As anew product, the compound of the GEORG KRANZLEIN. MAX HEYSE. PAULOCHWAT.

